CN103483548A - 一种低游离高相溶性聚氨酯固化剂的制备方法 - Google Patents
一种低游离高相溶性聚氨酯固化剂的制备方法 Download PDFInfo
- Publication number
- CN103483548A CN103483548A CN201310469710.4A CN201310469710A CN103483548A CN 103483548 A CN103483548 A CN 103483548A CN 201310469710 A CN201310469710 A CN 201310469710A CN 103483548 A CN103483548 A CN 103483548A
- Authority
- CN
- China
- Prior art keywords
- preparation
- curing agent
- ether
- polyurethane curing
- agent according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000004814 polyurethane Substances 0.000 title claims abstract description 21
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 20
- 238000010494 dissociation reaction Methods 0.000 title abstract 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000012948 isocyanate Substances 0.000 claims abstract description 12
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000009835 boiling Methods 0.000 claims abstract description 6
- -1 polyol ethers Chemical class 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229920001983 poloxamer Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims description 4
- WTXXSZUATXIAJO-OWBHPGMISA-N (Z)-14-methylpentadec-2-enoic acid Chemical compound CC(CCCCCCCCCC\C=C/C(=O)O)C WTXXSZUATXIAJO-OWBHPGMISA-N 0.000 claims description 4
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 4
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 4
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 3
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 3
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- PSBOOKLOXQFNPZ-UHFFFAOYSA-M lithium;2-hydroxybenzoate Chemical compound [Li+].OC1=CC=CC=C1C([O-])=O PSBOOKLOXQFNPZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical group CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003973 paint Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 206010015946 Eye irritation Diseases 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000013 eye irritation Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
- C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8029—Masked aromatic polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种低游离高相溶性聚氨酯固化剂的制备方法，先按质量份配好原料：(A)一种甲苯二异氰酸酯或两种甲苯二异氰酸酯的混合物，40～70份，(B)沸点≤200℃的酯类溶剂，23～27份，(C)三羟甲基丙烷，5～20份，(D)复合多元醇醚类物质，1～20份，(E)异氰酸酯三聚催化剂，0.1～0.2份，(F)异氰酸酯三聚阻聚剂，0.1～0.3份；本发明先利用不同的温度条件将大部分量的游离甲苯二异氰酸酯反应掉；然后通过将游离单体在催化剂的作用下发生三聚等反应，把剩余的游离甲苯二异氰酸酯单体去除，使制备出来的固化剂产物中游离甲苯二异氰酸酯含量达到最新国标要求，而且所得产物固含高、粘度低、相容性好、稳定性好、配漆后漆膜性能不变。
Description
技术领域
本发明涉及一种低游离高相溶性聚氨酯固化剂的制备方法。
背景技术
现市场上普遍使用的高固含75系列的聚氨酯固化剂中，以进口和国产为主。进口产品尤以拜耳公司的Desmodur L75为代表，该类产品通常采用薄膜蒸发法生产，利用高端进口设备-薄膜蒸馏器，将产品进行后期分离，使最终产品中游离甲苯二异氰酸酯(TDI)很低(通常在0.5以下)，从而达到环保低游离的效果。然而采用薄膜蒸发法设备投资较大，技术难度高，控制过程复杂，维护成本也很高，非一般企业所能接受。
目前国内生产低游离TDI聚氨酯固化剂产品的技术水平参差不齐，有的厂家因技术水平有限，甚至不能合成固体份质量份为75％的高固含固化剂，只能合成70％甚至以下的低固含固化剂。有的厂家能生产75系列固化剂，但生产出来的产品游离TDI(甲苯二异氰酸酯)单体含量较高，质量比达到5％以上，而甲苯二异氰酸酯单体有剧毒，过高的游离单体在施工过程中，对人体的呼吸系统、皮肤和眼睛刺激性较大，严重危害人体健康，不能达到国家的环保要求。还有的厂家技术水平较高，采用后期化学三聚方法能将游离TDI(甲苯二异氰酸酯)单体降低下来，但容易造成粘度大，相容性差，光泽变哑，活化期变短，贮存性变劣等不良影响，远远达不到进口75固化剂的效果。
发明内容
本发明的目的在于针对现有固化剂制备方法所存在的问题，提供一种低游离高相溶性聚氨酯固化剂的制备方法，该方法制备的产品具有低游离、低粘度、高固含及高相容性等性能，有效解决国内众多厂商难以解决的环保低游离与低粘高固含高相容不能兼得的技术难题。该方法不需要增加额外的投资和设备，不需要改变现有设备即可制得低游离高相溶性的产品，而且所制得的固化剂产品性能与原有相比不仅不受影响，在某些方面甚至更具优越性。
本发明的目的是这样实现的：
本发明的原料及用量为，(A)一种甲苯二异氰酸酯或两种甲苯二异氰酸酯的混合物，40～70份，(B)沸点≤200℃的酯类溶剂，23～27份，(C)三羟甲基丙烷，5～20份，(D)复合多元醇醚类物质，1～20份，(E)异氰酸酯三聚催化剂，0.1～0.2份，(F)异氰酸酯三聚阻聚剂，0.1～0.3份，以上份数均指质量份；制备步骤为，先将原料A、B投入反应釜，通氮气搅拌，升温至40-80℃的条件下，分2-5批投入原料C和D，冷却降温，温度保持在50～100℃条件下，反应4～8小时，检测NCO基团的质量百分含量，当它降至14～15时，降温加入原料E，保持在50～70℃下，反应1～5小时，检测NCO基团和游离甲苯二异氰酸酯的质量百分含量，当游离甲苯二异氰酸酯的质量百分含量≤1.5％时，立即加入原料F，搅拌均匀，降温至50℃以下，即可出料。
本发明中原料A为2，4-甲苯二异氰酸酯和2，6-甲苯二异氰酸酯的任意配比混合物。在混合物中，优选2，4-甲苯二异氰酸酯的质量百分含量在80％以上。
本发明中沸点≤200℃的酯类溶剂可选自下列之一：醋酸乙酯、醋酸正丙酯、醋酸异丙酯、醋酸丁酯、醋酸异丁酯、醋酸乙酯和醋酸丁酯的任意配比混合物。优选醋酸乙酯、醋酸丁酯、醋酸乙酯和醋酸丁酯的任意配比混合物。
本发明中复合多元醇醚类物质选自下列，1-丙醇、1-丁醇、正戊醇、正辛醇、2-辛醇、2-乙基-1-己醇、C12～C16脂肪醇、新戊二醇、1，2-丙二醇、1，3-丙二醇、1，4-丁二醇、1，3-丁二醇、乙二醇甲醚、乙二醇乙醚、乙二醇丁醚、二乙二醇甲醚、二乙二醇乙醚、二乙二醇丁醚。优选下列1-丁醇、正辛醇、2-乙基-1-己醇、C12～C16脂肪醇、新戊二醇、1，2-丙二醇、1，3-丁二醇、乙二醇丁醚或二乙二醇丁醚复合物。
本发明中异氰酸酯三聚催化剂选自下列之一：三正丁基膦、三烷基磷、叔胺、叔胺和苯基缩水甘油醚、三(二甲氨基甲基)-2，4，6-苯酚复配物、碱性的钾盐、钠盐和锂盐混合物、水杨酸锂加异辛酸亚锡、异辛酸锂加异辛酸亚锡或异辛酸锌。优选三(二甲氨基甲基)-2，4，6-苯酚复配物。
本发明中异氰酸酯三聚阻聚剂选自下列之一：无水氯化氢、硫酸、磷酸、双(2一乙基己基)磷酸氢盐或氯化苯甲酰，优选氯化苯甲酰。
本发明的有益技术效果在于：提供了一种反应体系，通过在体系中引入一种复合多元醇醚，对纯TDI-TMP加成物进行优化改良处理，利用合适的添加配比，降低产物的分子量，改善产物分子的极性，制备出粘度较稀，相容性较高的高固含产品。该方法合成出来的固化剂环保效应好，其固体份质量比达到75％或以上，游离TDI低于1.5％，配漆后能达到新国标GB18581-2009要求；在温度为25℃时，产品的旋转粘度为3000～4500cps，远低于目前市场产品的8000～10000cps；另外，常规产品与二甲苯容忍度一般在2.0以下(PU固化剂的一种测试方法)，本专利生产的产品与二甲苯的容忍度高达4.0左右，而且与常规树脂相容性极好，故称高相容性。配漆后的漆膜性能与进口75聚氨酯固化剂的性能基本相当，高端产品中可以部分取代，中低端产品中甚至可以全部取代。
其中，合成反应原理如下：
a).TDI+TMP加成反应：
b).TDI(以OCN-R-NCO表述)与复合多元醇醚(以R′OH表述)的反应(简式)：
OCN-R-NCO+R′OH→R′OOCNH-R-NHCOO R′
c).TDI(以OCN-R-NCO表述)的三聚化反应：
具体实施方式
作为本发明的具体的实施例一，可先称量好60％的甲苯二异氰酸酯、12％的三羟甲基丙烷、25％的乙酸乙酯、2.5％的复合多元醇醚类物质、0.2％的催化剂和0.3％的阻聚剂，然后按照上述方法制备，制出来的聚氨酯固化剂具有低游离、低粘度、高固含及高相容性可同时兼得的优点。
实施例二，可先称量好55％的甲苯二异氰酸酯、10％的三羟甲基丙烷、25％的乙酸乙酯、9.8％的复合多元醇醚类物质、0.1％的催化剂和0.1％的阻聚剂，然后按照上述方法制备。
实施例三，可先称量好50％的甲苯二异氰酸酯、8％的三羟甲基丙烷、25％的乙酸乙酯、16.7％的复合多元醇醚类物质、0.1％的催化剂和0.2％的阻聚剂，然后按照上述方法制备。
当然，以上实施例仅是用于对本发明的说明，本发明的具体应用并不仅限于例子中说到的应用，与本发明等同或衍生的技术方案也属于本发明的保护范围。
Claims (11)
1.一种低游离高相溶性聚氨酯固化剂的制备方法，其特征在于：先配备原料及用量为，(A)一种甲苯二异氰酸酯或两种甲苯二异氰酸酯的混合物，40～70份，(B)沸点≤200℃的酯类溶剂，23～27份，(C)三羟甲基丙烷，5～20份，(D)复合多元醇醚类物质，1～20份，(E)异氰酸酯三聚催化剂，0.1～0.2份，(F)异氰酸酯三聚阻聚剂，0.1～0.3份，以上份数均指质量份；制备步骤为，先将原料A、B投入反应釜，通氮气搅拌，升温至40-80℃的条件下，分2-5批投入原料C和D，冷却降温，温度保持在50～100℃条件下，反应4～8小时，检测NCO基团的质量百分含量，当它降至14％～15％时，降温加入原料E，保持在50～70℃下，反应1～5小时，检测NCO基团和游离甲苯二异氰酸酯的质量百分含量，当游离甲苯二异氰酸酯的质量百分含量≤1.5％时，立即加入原料F，搅拌均匀，降温至50℃以下，即可出料。
2.根据权利要求1所述的低游离高相溶性聚氨酯固化剂的制备方法，其特征在于：所述原料A为2，4-甲苯二异氰酸酯和2，6-甲苯二异氰酸酯的任意配比混合物。
3.根据权利要求2所述的低游离高相溶性聚氨酯固化剂的制备方法，其特征在于：所述原料A中2，4-甲苯二异氰酸酯的质量百分含量在80％以上的混合物。
4.根据权利要求1所述的低游离高相溶性聚氨酯固化剂的制备方法，其特征在于：所述沸点低于200℃的酯类溶剂选自下列之一，醋酸乙酯、醋酸正丙酯、醋酸丁酯、醋酸异丁酯、醋酸乙酯和醋酸丁酯的任意配比混合物。
5.根据权利要求4所述的低游离高相溶性聚氨酯固化剂的制备方法，其特征在于：所述沸点低于200℃的酯类溶剂优选醋酸乙酯、醋酸丁酯或醋酸乙酯和醋酸丁酯的任意配比混合物。
6.根据权利要求1所述的低游离高相溶性聚氨酯固化剂的制备方法，其特征在于：所述复合多元醇醚类物质选自下列，1-丙醇、1-丁醇、正戊醇、正辛醇、2-辛醇、2-乙基-1-己醇、C12～C16脂肪醇、新戊二醇、1，2-丙二醇、1，3-丙二醇、1，4-丁二醇、1，3-丁二醇、乙二醇甲醚、乙二醇乙醚、乙二醇丁醚、二乙二醇甲醚、二乙二醇乙醚、二乙二醇丁醚。
7.根据权利要求6所述的低游离高相溶性聚氨酯固化剂的制备方法，其特征在于：所述复合多元醇醚类物质为1-丁醇、正辛醇、2-乙基-1-己醇、C12～C16脂肪醇、新戊二醇、1，2-丙二醇、1，3-丁二醇、乙二醇丁醚或二乙二醇丁醚复合物。
8.根据权利要求1所述的低游离高相溶性聚氨酯固化剂的制备方法，其特征在于：所述异氰酸酯三聚催化剂为三正丁基膦、三烷基磷、叔胺、叔胺和苯基缩水甘油醚、三(二甲氨基甲基)-2，4，6-苯酚复配物、碱性的钾盐、钠盐和锂盐混合物、水杨酸锂加异辛酸亚锡、异辛酸锂加异辛酸亚锡或异辛酸锌。
9.根据权利要求8所述的低游离高相溶性聚氨酯固化剂的制备方法，其特征在于：所述异氰酸酯三聚催化剂为三(二甲氨基甲基)-2，4，6-苯酚复配物。
10.根据权利要求1所述的低游离高相溶性聚氨酯固化剂的制备方法，其特征在于：所述异氰酸酯三聚阻聚剂为无水氯化氢、硫酸、磷酸、双(2-乙基己基)磷酸氢盐或氯化苯甲酰。
11.根据权利要求10所述的低游离高相溶性聚氨酯固化剂的制备方法，其特征在于：所述异氰酸酯三聚阻聚剂为氯化苯甲酰。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310469710.4A CN103483548B (zh) | 2013-10-09 | 2013-10-09 | 一种低游离高相溶性聚氨酯固化剂的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310469710.4A CN103483548B (zh) | 2013-10-09 | 2013-10-09 | 一种低游离高相溶性聚氨酯固化剂的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103483548A true CN103483548A (zh) | 2014-01-01 |
| CN103483548B CN103483548B (zh) | 2016-03-09 |
Family
ID=49824178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310469710.4A Active CN103483548B (zh) | 2013-10-09 | 2013-10-09 | 一种低游离高相溶性聚氨酯固化剂的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103483548B (zh) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403085A (zh) * | 2014-11-26 | 2015-03-11 | 广东东旭化学工业制造有限公司 | 一种达欧标低游离哑光三聚体固化剂及其制备方法 |
| CN104610525A (zh) * | 2015-03-04 | 2015-05-13 | 南京通源新材料科技有限责任公司 | 一种无卤环保聚氨酯油性漆及其制备方法 |
| CN105131698A (zh) * | 2015-09-17 | 2015-12-09 | 广东聚盈化工有限公司 | 一种低游离tdi固化剂及制备方法 |
| CN105131249A (zh) * | 2015-09-17 | 2015-12-09 | 广东聚盈化工有限公司 | 一种高容忍度低游离tdi三聚体及制备方法 |
| CN105153388A (zh) * | 2015-09-17 | 2015-12-16 | 广东聚盈化工有限公司 | 一种单组份低游离tdi潮气聚氨酯固化剂及制备方法 |
| CN105949431A (zh) * | 2016-06-03 | 2016-09-21 | 滁州市龙飞化工有限公司 | 一种塑胶漆用聚氨酯固化剂的制备方法 |
| CN106046342A (zh) * | 2016-07-15 | 2016-10-26 | 赵前方 | 利用端氨基聚醚制备聚氨酯固化剂的方法 |
| CN108727560A (zh) * | 2018-04-19 | 2018-11-02 | 珠海联固化学工业有限公司 | 一种多羟基树脂改性的聚氨酯固化剂及其制备方法 |
| CN110092888A (zh) * | 2019-04-26 | 2019-08-06 | 同济大学 | 含氟异氰酸酯固化剂及其制备方法和应用 |
| CN111748076A (zh) * | 2020-07-23 | 2020-10-09 | 安徽江锐新材料有限公司 | 一种均质分散度高的丙烯酸聚氨酯固化剂及其制备方法 |
| CN113087679A (zh) * | 2020-01-08 | 2021-07-09 | 万华化学集团股份有限公司 | 一种低游离单体的多异氰酸酯固化剂、制备方法及涂料组合物和应用 |
| CN115850656A (zh) * | 2022-12-31 | 2023-03-28 | 韶关东森合成材料有限公司 | 一种高相容性低游离三聚体及其制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827346A (zh) * | 2012-09-17 | 2012-12-19 | 上海富臣化工有限公司 | 低游离甲苯二异氰酸酯聚氨酯固化剂及其制备方法 |
-
2013
- 2013-10-09 CN CN201310469710.4A patent/CN103483548B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827346A (zh) * | 2012-09-17 | 2012-12-19 | 上海富臣化工有限公司 | 低游离甲苯二异氰酸酯聚氨酯固化剂及其制备方法 |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403085A (zh) * | 2014-11-26 | 2015-03-11 | 广东东旭化学工业制造有限公司 | 一种达欧标低游离哑光三聚体固化剂及其制备方法 |
| CN104610525A (zh) * | 2015-03-04 | 2015-05-13 | 南京通源新材料科技有限责任公司 | 一种无卤环保聚氨酯油性漆及其制备方法 |
| CN105131698A (zh) * | 2015-09-17 | 2015-12-09 | 广东聚盈化工有限公司 | 一种低游离tdi固化剂及制备方法 |
| CN105131249A (zh) * | 2015-09-17 | 2015-12-09 | 广东聚盈化工有限公司 | 一种高容忍度低游离tdi三聚体及制备方法 |
| CN105153388A (zh) * | 2015-09-17 | 2015-12-16 | 广东聚盈化工有限公司 | 一种单组份低游离tdi潮气聚氨酯固化剂及制备方法 |
| CN105949431A (zh) * | 2016-06-03 | 2016-09-21 | 滁州市龙飞化工有限公司 | 一种塑胶漆用聚氨酯固化剂的制备方法 |
| CN106046342A (zh) * | 2016-07-15 | 2016-10-26 | 赵前方 | 利用端氨基聚醚制备聚氨酯固化剂的方法 |
| CN108727560A (zh) * | 2018-04-19 | 2018-11-02 | 珠海联固化学工业有限公司 | 一种多羟基树脂改性的聚氨酯固化剂及其制备方法 |
| CN110092888A (zh) * | 2019-04-26 | 2019-08-06 | 同济大学 | 含氟异氰酸酯固化剂及其制备方法和应用 |
| CN113087679A (zh) * | 2020-01-08 | 2021-07-09 | 万华化学集团股份有限公司 | 一种低游离单体的多异氰酸酯固化剂、制备方法及涂料组合物和应用 |
| CN111748076A (zh) * | 2020-07-23 | 2020-10-09 | 安徽江锐新材料有限公司 | 一种均质分散度高的丙烯酸聚氨酯固化剂及其制备方法 |
| CN115850656A (zh) * | 2022-12-31 | 2023-03-28 | 韶关东森合成材料有限公司 | 一种高相容性低游离三聚体及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103483548B (zh) | 2016-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103483548B (zh) | 一种低游离高相溶性聚氨酯固化剂的制备方法 | |
| CN104086738B (zh) | 无溶剂环保聚氨酯汽车革面层树脂及其制备方法和应用 | |
| CN101481449B (zh) | 湿式高耐水解合成革用含浸聚氨酯树脂及其制造方法 | |
| CN102827570B (zh) | 一种高固含量鞋用水性胶黏剂及其制备方法 | |
| CN105001701B (zh) | 用于亚光漆的高固含均分子量无毒聚氨酯固化剂及其制法 | |
| CN105061711B (zh) | 一种端基为环氧基的dopo型反应型阻燃剂及其制备方法和应用 | |
| CN104140520B (zh) | 一种超软质高弹性耐水解高剥离的湿式聚氨酯树脂及其制备方法 | |
| CN102942664A (zh) | 一种端羟基超支化聚氨酯的制备方法 | |
| WO2009002100A3 (en) | Polyol included phosphorus and nitrogen | |
| CN101857721A (zh) | 一种耐寒、耐溶剂性不黄变聚氨酯树脂及其制备方法 | |
| CN1826364A (zh) | 含脲二酮基的羟基终端的聚氨酯组合物 | |
| CN101319129A (zh) | 单组分无溶剂湿气固化聚氨酯胶粘剂及其制造方法 | |
| TWI509016B (zh) | 環氧樹脂組合物 | |
| CN103881048B (zh) | 一种树枝状水性聚氨酯的制备方法 | |
| CN105238014B (zh) | 单组分高固含聚氨酯树脂及其制备方法和应用 | |
| CN103159910A (zh) | 一种具有高相变焓的聚氨酯固―固相变材料的制备方法 | |
| CN102070762B (zh) | 含膦酸盐亲水基团的水性聚氨酯分散体的合成工艺 | |
| CN102617827B (zh) | 一种固化剂改性1，6-己二异氰酸酯缩二脲及其制备方法 | |
| CN105399937A (zh) | 一种聚酯多元醇的制备方法 | |
| JP6266782B2 (ja) | ウレトジオン基を含むイソシアネートホモ重合体の調製方法 | |
| CN105754070A (zh) | 一种低游离tdi三聚体固化剂及其制备方法 | |
| CN102391821B (zh) | 植珠用水性聚氨酯胶黏剂及其制备方法 | |
| CN101870858A (zh) | 一种低成本粘合剂及其制备方法 | |
| CN102675585B (zh) | 添加醇胺化合物的聚氨酯微孔弹性体及制备方法和应用 | |
| EP3288993B1 (de) | Polyurethanummantelungen mit verminderter wasseraufnahme und deren verwendung |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: Jianye Road, 529700 Guangdong city of Heshan Province Yao town Applicant after: GUANGDONG DOXU CHEMICAL INDUSTRY MANUFACTURING Co.,Ltd. Address before: Jianye Road, 529700 Guangdong city of Heshan Province Yao town Applicant before: HESHAN DOXU CHEMICAL INDUSTRY MANUFACTURING Co.,Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: HESHAN DOXU CHEMICAL INDUSTRY MANUFACTURING CO., LTD. TO: GUANGDONG DOXU CHEMICAL INDUSTRY MANUFACTURING CO., LTD. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chen Aiwen Inventor after: Qin Yongyu Inventor after: Li Qingliang Inventor before: Liu Lingyun |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170626 Address after: 519050 Guangdong city in Zhuhai Province, South Town Gaolan Port Economic Zone surge Road No. 5 Patentee after: ZHUHAI LIANGU CHEMICAL INDUSTRY CO.,LTD. Address before: Jianye Road, 529700 Guangdong city of Heshan Province Yao town Patentee before: GUANGDONG DOXU CHEMICAL INDUSTRY MANUFACTURING Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191029 Address after: 529724 Jianye Avenue, Heshan Yayao Town, Jiangmen City, Guangdong Province Patentee after: GUANGDONG DOXU CHEMICAL INDUSTRY MANUFACTURING Co.,Ltd. Address before: 519050 Guangdong city in Zhuhai Province, South Town Gaolan Port Economic Zone surge Road No. 5 Patentee before: ZHUHAI LIANGU CHEMICAL INDUSTRY CO.,LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230118 Address after: 512529 B28-29, Huacai Chemical Coating City, Wengyuan County, Shaoguan City, Guangdong Province Patentee after: Shaoguan Dongsen synthetic materials Co.,Ltd. Address before: 529724 Jianye Avenue, Yayao Town, Heshan, Jiangmen City, Guangdong Province Patentee before: GUANGDONG DOXU CHEMICAL INDUSTRY MANUFACTURING Co.,Ltd. |